Method for recovering alcohol from alcoholic mixtures



Ap 28, 1942. n. E. KNAPP ErAL METHOD FOR RECOVERING ALCOHOL FROM ALGOHOLIG MIXTURES Filed April 6, 1940 Patente'd pr. 28, 1942 METHOD FOR RECOVERING ALCOHOL FROM ALCOHOLIC MIXTURES Ismond E. Knapp, Robert E. Price and Herman vA. Brondum, Picayune, Miss., assignors to Crosby Naval Stores, Incorporated, Picayune,

Miss., a corporation of Mississippi Application April 6, 1940, Serial No.'328,386

' (c1. 2oz- 60) 6 Claims.

The present invention relates to an improved method of recovering substantially pure alcohols from alcoholic mixtures containing varying proportions of hydrocarbon solvents, and is more particularly concerned with the 'recovery of water-soluble alcohols from .ternary mixtures of the latter with hydrocarbons and water. In its more specific aspect the invention contemplates and provides an improved method of recovering substantially pure ethyl alcohol of from 93 to 95% strength from alcoholic mixtures of rosin,

' These adsorption agents in time become saturated With rosin impurities and/or color bodies, and it becomes necessary in the commercial operationV of such a process to revivify or restore the adsorptive material to its original condition.n

This may be done, as more fully described hereinafter, by treating the adsorptive material either with a mixed organic solvent such as a mixture of ethyl alcohol and petroleum naphtha, or with ethyl alcohol alone. In any case the revivication solvent dissolves the rosin impurities and/or color bodies (conveniently referred to here merely as rosin impurities) off the adsorbent. A solution of rosin impuritiesis thus obtained from which the revivication solvent must be recovered for further use in the'process.

In use today there are at least two commercial processes in which the impure rosin solution is percolated through a. tower of an adsorption agent until the latter is saturated with rosin impurities and then the adsorption agent is subsequently` treated or revivified byushing the tower with various solvents. One of these processes employs dehydrated fullers earth as an adsorption medium and the revivification is carried out through the use of an `anhydrous mixed organic solvent, such as a mixture of anhydrous ethyl alcohol and petroleum naphtha. In this process special precautions are taken to prevent access of water to the system and the alcoholnaphtha-rosin impurities solution must be maintained in a practically anhydrous condition. By so doing advantage is taken of the well-known `1act that anhydrous ethyl alcohol and naphtha form an azeotropic mixturey so that the alcoholnaphtha-rosin impurities solution is simply run into a still or evaporator and subjected to distillation. The distillate consists of a mixture of alcohol and naphtha in the proportion of approximately 35 parts of ethyl alcohol to 65 parts of naphtha. The naphtha being present in excess, this 35-65 mixture continues to distill over until all the alcohol Vhas been recovered from the solution. Since the solution is substantially free of water, this 35-65 mixture is obtained as a homogeneous liquid distillate which .is re-used for revivication as if it were a single solvent.

As stated, the process is advantageous because the solvent mixture is azeotropic and may be recovered by simple distillation. On the other hand', the fact that the entire system must be maintained in a substantially anhydrous condition renders the whole process economically unattractive.

Another commercial process (hereinafter referred to as the Price process) is carried out substantially in accordance with the disclosure in U. S. Patent No. 2,181,791 to R. E. Price and the solvent recovery system of the present invention is particularly adapted to the rosin purification process of this Price patent. In practical operation the Price process, employing magnesium silicate as the adsorbent medium, need not be carried out under anhydrous conditions. Consequently, the magnesium silicate is not dehydrated and the revivication solvent is ordinary, inexpensive, commercial 93 to 95% lethyl alcohol. This is a distinct advantage over the aforementioned process employing dehydrated fullers earth and an anhydrous revivication solvent.

After the adsorbent in a percolation tower of the Price process has become suciently saturated with rosin impurities, the naphtha solution of the rosin which is being purified is displaced with fresh naphtha. This in turn is displaced by pumping warm alcohol through the tower which dissolves the rosin impurities oi the adsorbent. This solution of rosin impurities in alcohol is displaced with more alcohol which acts as a wash or a rinse, and it in turn is displaced by pumping in fresh naphtha which is preferably preheated to say 'l0-100 C. in order to insure the removal of all the alcohol from the adsorbent. The alcohol-rosin impurities solution is pumped to a .suitable tank which acts as a feed tank for a suitable still or evaporator. It is essential that no alcohol remain in the tower for if it did, it would later appear in the naphtha solution of the dark rosin which is being decolorized and would then greatly 'lower the eiciency of the adsorption agent. In order to keep all alcohol out of the naphtha or naphtharosin solution, it is customary to regulate the valves on the towers and pumps so that some naphtha is pumped into the alcohol-rosin impurities feed tank. This is purely a precautionary measure, and it will be readily understood by one skilled in the art that pumping some naphtha into the 'alcohol-rosin impurities tank is the simplest way of ushing out the pipe lines, pumps, and towers, etc., and eliminating the danger of contaminating the rosin-naphtha solution with alcohol. In actual plant operation the net result is that the alcohol-rosin impurities solution in the evaporation feed tank may contain as much as 30 to 40% of naphtha. The problem and prime object of the present invention, therefore, is to recover the alcohol from this solution.

It should be pointed out that in describing the present invention, the word solution is not used in the true sense of that term. Because of the presence of water, the naphtha-alcohol rosin impurities actually form, with the water, a mixture rather than a true solution. In other words, after revivication, the material in the evaporation feed tank from which the alcohol is to be recovered consists of a mixture of alcohol, water, naphtha, and rosin impurities. This mixture is formed by the collection of the fluids which are successively passed through the towers in the revivication process, and at no time is there ever a true solution of alcohol and naphtha either inthe towers or in the evaporation feed tank.

Since the alcohol used in the revivication contained from 5 to '7% water, this water will be present in the alcohol-naphtha-rosin impurities solution, and if this solution is subjected to distillation, the water -will vaporize and come over with the alcohol and naphtha. Although anhydrous ethyl alcool and naphtha are readily and completely miscible in all proportions to give a true solution, as above explained, this is not the case with 93-95% ethyl alcohol and naphtha. Such a mixture separates into two layers, the

upp'er one being-predominantly naphtha with a relatively small amount, say approximately l0 to 15% at ordinary room temperature, of alcohol dissolved in it, whereas the lower layer is predominantly alcohol with a considerable proportion, say up to 40% or more, of naphtha dissolved in it. The partition. of the two solvents between the two layers is dependent on their relative proportions in the total mixture, on the temperature, and on the percentage of water present. 'I'he composition of the distillate from the alcohol-naphha-rosin impurities solution, if subjected to simple distillation, is such that it separates into two layers, both of which are mixtures of alcohol and naphtha in varying proportions.

It is known that alcohol, water, and naphtha form a ternary mixture which boils at a temperature lower than that of any one of its three components, namely at approximately 'Z3-74 C. under '760 mm. pressure. If only small amounts of water and naphtha are mixed with a. large volume of alcohol, the ternary mixture will distill over rst and will continue until all the water has been vaporized. 'I'hen a mixture of anhydrous ethyl alcohol and naphtha will distill over until the naphtha has been removed, and finally anhydrous ethyl alcohol will come over. It is practically impossible, however, to obtain alcohol free from naphth'a by the simple distillation of the alcohol-naphtha-rosin impurities solution. This is due tothe fact that there is too the alcohol by means of the ternary mixture above mentioned. What actually happens is that the alcohol, naphtha and water all distill over and then the distillate separates into two layers, neither of which is pure alcohol or alcohol free from naphtha. These layers can be separated by gravity, and each layer re-distilled through an eicient fractionating column but even then the alcohol recovered will not be free from naphtha.

It is essential, therefore, to the successful commercial operation of the Price process that a. method be devised by which the alcohol can be eflciently recovered from the alcohol-naphtharosin impurities solution. We have discovered such a method and have' found that it works very satisfactorily on plant scale. Essentially our process consists lin distilling the alcoholnaphtha-rosin impurities solution continuously and showering cold water into the mixed vapors as they pass into a condenser. The condensate, consisting of alcohol, naphtha and a considerable volume of water, is run through a mixing vessel into a suitable separator. The ilow of water is so regulated that the volume added is approximately equal to the volume of alcohol distilling, with the result that the lower layer in the sparator is approximately Il5-50% alcohol and 50-55% water. Under these conditions, the separation of the naphtha is practically quantitative, and when the top layer (naphtha) is decanted from the separator it is substantially free from alcohol, in

fact it contains ordinarily not more than a trace of alcohol. This is suitable for re-use without further treatment. If the apparatus used provides eicient contact, mixing and separation, the lower layer will contain no naphtha. This lower layer is run to a continuous fractionating column in which the alcohol taken oi overhead shows no naphtha and analyzes 93 to 95% ethyl alcohol. It is re-used as a revivification solvent.' The water, of course, is lost as slop to the sewer.

In order to illustrate our invention more clearly we show in the accompanying drawing a diagrammatic layout of equipment which we have found satisfactory for effecting the recovery of alcohol from a solution of rosin impurities in alcohol, containing a variable percentage of naphtha.

The rosin impurities-alcohol-naphtha solution from the revivied towers is accumulated in a suitable evaporation feed tank I and by means of a pump 2 it is pumped to a, steam-heated vertical-tube evaporator 3. The mixed alcohol and naphtha vapors leave the evaporator through pipe 4 and pass into condenser 5. This is a tubular water-cooled condenser of conventional type but in the vapor space above the tube-sheet there is inserted a spray nozzle 6 through which cold water is pumped. This water spray mixes intimately with the alcohol and naphtha vapors as they condense. 4

The concentrated rosin impurities-alcoholnaphtha solution passes from evaporator 3 through pipe 1 to another evaporator 8. Rosin impurities leave this evaporator through pipe I2. As before, the alcohol and naphtha vapors pass into condenser 9 which is equipped with a water spray I0 similar to spray 6 in the 'top of condenser 5.

The mixture of alcohol, water and naphtha leaves condensers 5 and 9 and passes through pipe II into a mixing vessel I3, from which it overflows into separator I4. Here the mixed liquids separate by gravity and-the naphtha rises to the top and overows into naphtha storage tank l5. The alcohol-water layer settles to the bottom of the separator and passes into dilute alcohol feed tank I6. From here it passes into continuous alcohol still I1. The recovered alcohol is condensed in condenser I8 and passes through cooler I9 intov alcohol storage tank 20. The water is drawn off the bottom of the still Il and goes to the sewer through pipe 2 I.

It is to be understood that many variations can be made in the arrangement of apparatus, piping, etc., without departing from the essence offour invention. For example, the water may be added to the alcohol-naphtha mixture after condensation and the mixture pumped through pipes in which there are propeller type agitators.

Another procedure which we have used on a large scale is to run the alcohol-naphtha lcondensate into the bottom of an upright tank containing water. A variation of this procedure is to have a series of baille plates in the mixing tank and to pump a stream of water into the tank along with the alcohol-naphtha condensate allowing the mixture to, overow from the mixing tank to a suitable separator. Other variations of effecting intimate contact between water and the alcoholnaphtha condensate may be used but we have found that by contacting the alcohol-naphtha mixture in the vapor phase with water in a manner described above provides the most rapid and generally eilcient method.

It is also obvious that the use of a continuous still is not essential to the recovery of alcohol according to our invention. For example, the alcohol-water layer from the separator can be run into a storage tank of a suitable size and then can be distilled in batches in a suitable still equipped`with an eiiicient frac-tionating column.

It is also to be understood that this method of recovery of alcohol from an alcohol-rosin impurities solution containing naphtha is not limited to ethyl alcohol. We have found that our method a substantially pure alcohol from a mixture of the alcohol, water and a petroleum hydrocarbon which comprises distilling the mixture, continuously contacting the alcohol-petroleum hydrocarbon vapors with water, continuously collecting and settling the resulting diluted alcoholpetroleum hydrocarbon condensate'to form layers, separating the resulting substantially pure petroleum hydrocarbon layer from the alcohol- Water layer, continuously distilling the latter layer and recovering substantially pure alcohol.

3. A process for separating and recovering a substantially pure alcohol from a mixture of the alcohol, water and a petroleum hydrocarbon which comprises distilling the mixture, contacting the alcohol-petroleum hydrocarbon vapors with water, collecting and settling the resulting diluted alcohol-petroleum hydrocarbon condensate to form layers, separating the layer of substantially pure petroleum hydrocarbon, distilling the alcohol-water layer and recovering subtha, distilling the lower ethyl alcohol-water layer and recovering substantially pure SiS-95% ethyl alcohol. l,

5. In a process for revivifying adsorbent beds l contaminated with wood rosin impurities whereis also applicable to other water-soluble alcohols,

such as methyl alcohol and iso-propyl alcohol.

Our invention, furthermore, is not limited to the separation of water-soluble alcohols from any particular petroleum naphtha. Since the method does not depend upon any speciiic difference in the boiling points or vapor pressures of the two solvents to be separated, it can be applied to mixtures of alcohol with various petroleum hydrocarbon solvents, such as extraction naphthas, varnish makers and painters naphthas, the so-called Stoddard Solvent, mineral spirits, thinners, gasolinas, etc. The method also is applicable to alcoholic solutions containing a variable percentage of aromatic hydrocarbons such as benzene, toluene and the like.

What we claim is:

1. A p ocess for separating and recovering substantia'ly `pure ethyl alcohol of 93-95% strength from a mixture of ethyl alcohol, water and naphtha which comprises distilling the mixture, contacting the alcohol-naphtha vapors with water, collecting and settling the resulting diluted alcohol-naptha condensate to form layers, separating the layer of substantially pure naphtha, distilling the ethyl alcohol-water layer, and

in the bed is ushed with 9395% ethyl alcohol,

the alcohol, is displaced from the bed by ushing prises distilling the collected mixture, contacting the alcohol-@phtha vapors with water, collecting and settling the resulting diluted alcoholpetroleum hydrocarbon condensate to form layers, separating the upper layer of substantially purenaphtha, and distilling the lower ethyl alcohol-water layer tov recover substantially pure 93-95% ethyl alcohol in a condition which may be returnedto a contaminated adsorbent bed for further revivificatlon. V

6. A process for separating and recovering a substantially pure alcohol from a mixture of the alcohol, water and a petroleum' hydrocarbon, which comprises distilling the mixture, contact- "ing the alcohol-petroleum hydrocarbon vapors with water in the form of a spray to mix a volume of water with the alcohol-petroleum naphtha vapors in an amount atleast approximately equal to' the volume of alcohol being distilled and condensed, collecting andvsettling the condensate to form layers, separating the layer of substantially pure petroleum hydrocarbon, distilling the alcohol-water layer and recovering substantially pure alcohol'. v

IsMoND E. KNAPP. ROBERT E. PRICE. HERMAN A. BRONDUM. 

